Method of preparing lipoproteins from fatty acids present in olive oil

ABSTRACT

A method of preparing lipoproteins, lipoaminoacids, lipid esters, and glucolipids from olive oil or one or more of its constituting fatty acids which are condensed with vegetal protein hydrolyzates or aminoacids or esterificated with alcohols or sugars, said fatty acids being chlorinated fatty acids of the olive oil.

FIELD OF THE INVENTION

The present invention relates to a method of preparing a set ofsubstances having new characteristics for use especially in theproduction of a very large range of products such as cosmetics, drugs,foods (emulsions, creams, milks, ointments, shampoos, cleansing meansfor face/body, bath foams, etc.) industrial products (detergents forwashing-machines, dishwashing machines, all-purpose cleansing agents),and chemical-pharmaceutical products (solvents, dispersing agents,emulsifiers for aerosol, inhalations, environment deodorizers).

These preparations can be used under absolute safety conditionsregarding both toxicological-allergic and environment-friendly aspectssince their constituents are already present in nature.

SUMMARY OF THE INVENTION

The products prepared by the method according to the invention can beconsidered to belong to four main groups, namely lipoproteins,lipoaminoacids, lipid esters, and glucolipids.

The preparation of such groups starts from chlorides of fatty acids,particularly the individual fatty acids forming the olive oil or amixture of such fatty acids.

Among the fatty acids of the olive oil used individually or incombination in the method according to the invention oleic acid,palmitic acid, myristic acid, and stearic acid have the greatestimportance. Such acids are condensed with vegetal protein hydrolysatesto provide lipoproteins, with aminoacids to provide lipoaminoacids, withalcohols to provide lipid esters, and with sugars to provideglucolipids.

BEST MODE OF CARRYING OUT THE INVENTION

Some examples of the method according to the invention will be describedherebelow.

In a preferred embodiment of the method of preparing a lipoprotein offully vegetal nature with a large range of applications, as explainedthereafter, the following steps are carried out by using a hydrolyzedvegetal protein, namely wheat gluten which is enzymatically hydrolyzed,in the condensation of the fatty acids of olive oil:

An enzymatic hydrolyzate solution of wheat gluten (60-80% by weightreferred to the finished product) is fed into a mixer of stainless steeland brought to a temperature between 45° C. and 70° C.; the followingsubstances in the indicated proportions are added under stirring:

L.ascorbic acid 0.1-0.4% glycerol   4-11%

and 2-4% potassium hydrate or sodium hydrate water solution having aconcentration between 20 and 35% until a pH between 7.5 and 9.5 isreached while keeping the temperature at the initial value.

More particularly a substance with optimum characteristics is obtainedby carrying out the following Example.

An amount of gluten hydrolisate equal to 70% by weight of the finishedproduct is fed into a mixer of stainless steel and heated at 55° C.under stirring. When such temperature is reached, 0.3% L. ascorbic acid,0.3% sodium EDTA, 10% glycerol, and 30% potassium hydrate (KOH) watersolution are added until pH 8.5 is reached.

After about 15 minutes the reaction is started by adding 6% by weight ofchlorinated fatty acids of olive oil still under stirring at constanttemperature and the above pH 8.5 which is kept by a continuous, verygradual addition of 8% potassium hydrate solution (30% water solution) .The reaction is continued under stirring at constant temperature forabout 2 hours followed by a slow cooling. Finally, pH is adjusted to 7by adding a total amount of 1% phosphoric acid and citric acid in aratio of 1:1.

In order to obtain a lipoaminoacid to be used according to theapplications of the present invention, the following method has beencarried out by using a derivative of glutamic acid as aminoacid, namelysodium glutamate, and employing the following substances in theindicated weight proportion ranges: An amount of 30-42% distilled water,10-17% sodium glutamate, 0.1-0.5% sodium EDTA, 8-11% 95°-ethyl alcoholare mixed in a reactor of stainless steel. Under stirring the mixture isbrought to a temperature between 45° C. and 75° C. by adding verygradually an amount of 12-20% of a 30% potassium hydrate water solutionand 16-25% chlorinated fatty acids of olive oil taking care of keepingpH between 8 and 12 and the temperature at the initial value. Thereaction is continued for 2 to 5 hours followed by a cooling of thewhole mixture and citric acid is added to adjust pH to 7-8. Finally,ethyl alcohol is distilled and the balance to 100 is formed by addingdistilled water.

Therefore, a lipoaminoacid having essentially the same characteristicsas the lipoprotein both as far as its essential features andapplications is concerned but capable of producing a persistent, creamy,more abundant foam has been prepared by the above-mentioned method.

A lipoaminoacid having the desired characteristics to an optimum extenthas been prepared by reacting the above-mentioned substances asindicated above in the amounts of the following Example:

Example of Lipoaminoacid:

In a reactor of stainless steel the following substances are mixed:

Distilled water 36, 7% Sodium glutamate 14% Sodium EDTA 0.3% 95°-Ethylalcohol 10%

The mixture contained in the reactor is brought to 65° C. under stirringand:

30% KOH water solution 17% Chlorinated fatty acids of olive oil 21%

are gradually added still under stirring and keeping pH to 9.5.

The reaction is continued for 3 hours and after cooling citric acid isadded until pH 7.5 is reached. Finally, ethyl alcohol is distilled andthe balance to 100 of the final product is formed by adding distilledwater.

In order to obtain a lipid ester to be used according to theapplications of the invention, the following method has been carried outby using a fatty alcohol, namely oleic alcohol, and employing thefollowing substances in the indicated weight proportion ranges: Oleicalcohol is fed into a reactor of stainless steel provided with stirrerand distiller and, after having brought the temperature to 60-96° C.,chlorinated oleic acid is added, the ratio between oleic alcohol andoleic acid being 1:0.8-1:1.5. HCl fumes developed during the reactionare then recovered by feeding them to a separated alkali solution.

It should be noted that the addition of chlorinated oleic acid must begradual and very slow so as to be concluded in a period of 2-5 hours.The reaction is continued for 3-5 hours by keeping the initialtemperature constant. The distillation of the hydrochloric acid shouldbe complete. A washing is carried out in the end by mixing withdistilled water in a proportion of about 20% of the total mass that iseventually discharged from the bottom of the reactor.

A lipid ester having essentially the desired characteristics wasprepared by the above-mentioned method.

A lipid ester essentially having the desired characteristics wasprepared by reacting the above-mentioned substances according to thedescribed method in the amounts listed in the following Example:

Example of Lipid Ester:

Under the above-mentioned conditions oleic alcohol adjusted to 90° andchlorinated oleic alcohol in the ratio of 1:1.1 are fed by adding thelatter very slowly during 4 hours into a reactor of stainless steelprovided with stirrer and distillator. The mixture is reacted for afurther 4 hours still at temperature of 90° C. under distillation of thehydrochloric acid by conveying the HCl fumes to an alkali solution. Thewashing with 20% distilled water is carried out at the end of thedistillation, as indicated above.

By the Example described above a light, clear, colourless, stable to theoxidation, non-fatty oil is obtained so that quite soft, delicatecosmetics and dermatologic products, oils, emulsions, lipogels etc.provided with excellent feel, softness and dermic compatibility can beprepared.

In the following method the chlorides of the olive oil acids arecondensed with sugars derived, for example, from enzymatic hydrolysis ofstarch, barley, wheat and the like.

In order to prepare a glucolipid to be used according to theapplications of the present invention, the following method has beencarried out by using tetraose malt as sugar and employing the followingsubstances in the indicated weight-proportion ranges: An amount of38-45% distilled water and 18-36% tetraose malt produced by enzymatichydrolysis of a starch are fed into a reactor of stainless steel; anamount of 9-18% 95°-ethyl alcohol referred to the finished product isadded under stirring and the whole : mixture is brought to a temperaturebetween 45 and 75° C. by adding 0.1-0.5% sodium EDTA and then verygradually 7-15% chlorinated oleic acid and 3-7% of a 30%-solution ofsodium hydrate taking care of keeping pH between 7 and 9.

The reaction is continued for 2-5 hours still under stirring at theinitial temperature. Final pH is adjusted between 6 and 8 and alcohol isdistilled forming the balance to 100 by adding distilled water. Aglucolipid having the desired characteristics to an optimum extent hasbeen prepared by reacting the above-mentioned substances as indicatedabove in the amounts of the following Example:

Example of glucolipid:

In a reactor of stainless steel the following substances are mixed:

Distilled water 46% Tetraose malt 24% 95°-Ethyl alcohol 15% Sodium EDTA0.3%

Still under stirring and bringing the content of the reactor to atemperature of 65° C. an amount of 10% chlorinated oleic acid and 4.5%of a 30% NaOH water solution are gradually added keeping pH to 8.5.

The reaction is continued for 3 hours and thirty minutes and citric acidis added under constant temperature until pH 7.5 is reached. Finally,ethyl alcohol is distilled and the balance to 100 of the final productis formed by adding distilled water.

INDUSTRIAL APPLICABILITY

The finished product showed eudermic properties perfectly tolerated alsoby the most delicate skins and the mucosa. Furthermore it has hydrating,emollient, protective properties and, as far as its inherent cleansingactivity is concerned, it is also suitable for the preparation ofcleansing creams and milks, shampoos, bath foams, personal cleanlinessproducts and, more particularly, paedocosmetics.

What is claimed is:
 1. A method of preparing a mixture of lipoproteinscomprising the steps of: (a) reacting a first mixture of chlorinatedfatty acids of olive oil with a second mixture comprising a vegetalprotein hydrolyzate for a time and under conditions effective to form amixture of lipoproteins, wherein said mixture of chlorinated fatty acidsis obtained by chlorinating a mixture of all fatty acids present inolive oil; and (b) isolating the mixture of lipoproteins of step (a). 2.The method according to claim 1 for preparing a mixture of lipoproteinscomprising the steps of: (a) introducing an enzymatic hydrolyzatesolution of a vegetable protein into a mixer; (b) setting thetemperature of the enzymatic hydrolyzate solution to 45° C.-75° C.; (c)adding L-ascorbic acid and glycerol to a final concentration of about0.1-0.4% and 4-11%, respectively; (d) adjusting the pH of the resultingsolution from steps (a), (b) and (c) to 7.5-9.5 by adding an aqueoussolution of 20-35% KOH or NaOH to the solution while maintaining thetemperature within the range of 45-70° C.; (e) adding the chlorinatedfatty acids of olive oil to the solution of step (d); (f) reacting thechlorinated fatty acids of olive oil and hydrolyzed vegetable proteinfor a time and under conditions to form a mixture of lipoproteinreaction products; and (g) isolating the resulting lipoprotein reactionproduct mixture.
 3. A method for preparing a mixture of lipoproteinscomprising the steps of: (a) obtaining a hydrolyzate solution byenzymatic hydrolysis of gluten; (b) setting the gluten hydrolyzate to atemperature of about 55° C. with stirring; (c) adding L-ascorbic acidand glycerol in an amount to a final concentration of about 0.30% and10%, respectively, and further adding sodium ethylene diaminetetraacetic acid in an amount of about 0.3%; (d) adding a solution of30% KOH in water solution until a pH of 8.5 is reached; (e) stirring theresulting mixture for 15 minutes and then adding chlorinated fatty acidsof olive oil under stirring in an amount in a final concentration ofabout 6% by weight and keeping the temperature and pH constant byfurther adding continuously and gradually a 30% KOH water solution in anamount of about 8% of the reaction mixture; (f) continuing the reactionunder stirring at a constant temperature for about 2 hours followed byslow cooling; (e) adjusting the pH of the mixture to about 7 by addingphosphoric acid and citric acid in a ratio of 1:1; and (h) isolating themixture of lipoproteins from the reaction product mixture.
 4. The methodaccording to claim 3 wherein the weight ratio of protein to fatty acylgroup in the lipoprotein is 70:30.